CN100340589C - Thermoplastic containers exhibiting excellent protection to various ultraviolet susceptible compounds - Google Patents

Abstract

Novel ultraviolet absorbing compounds that are liquid in nature, are extremely low in color (and thus permit use without the concomitant necessity of adding large amounts of other coloring agents to combat such discoloring), and are highly effective in providing protection in wavelength ranges for which previous attempts at low-color ultraviolet absorbers have failed are provided herein. Such compounds provide such excellent, inexpensive, and beneficial protection from ultraviolet exposure within various media, including, but not limited to, clear thermoplastics. The particular compounds are generally polymeric in nature including various chain lengths of polyoxyalkylenes thereon and are liquid in nature to facilitate handling and introduction within the target media. In addition, such ultraviolet absorbers also exhibit extremely low migratory properties thereby providing long-term protective benefits to the target media as well. This invention also concerns the end products, specific broadly defined types of compounds providing such beneficial characteristics, methods of making such low-color compounds, and methods of producing such clear, UV protected end products.

Description

The low-color ultraviolet absorption agent that high wavelength ultraviolet protection is used

Invention field

The present invention relates to normality is the new ultra-violet line absorption compound of liquid; their colours (color) are extremely low (and can be therefore at the seal slurry; needn't add a large amount of other tinting materials in the colourless application to resist any decolouring); and they provide efficient protection for some wavelength region, and these wavelength regions were protected it with the low-color ultraviolet absorption agent in the past and do not succeeded.In non-exclusively comprising the various media of transparent plastics, this compounds provides excellent, cheap and useful ultraviolet irradiation protection.Concrete compound in fact generally is a polymkeric substance, comprises the polyoxyalkylene of various chain lengths thereon, and normality is liquid, so that operation and importing in the destination media.In addition, this class UV light absorber also presents extremely low transport property, can be destination media whereby long-effective protection is provided simultaneously.The invention still further relates to the finished product, the compound of the specific broad types of these beneficial characteristics is provided, the production method of the finished product of the method for making of these low colour compounds and this limpid, antiultraviolet.

Background technology

All United States Patent (USP)s that this specification sheets is from first to last quoted are incorporated the present invention in this integral body.

The ultraviolet radiation absorption immunomodulator compounds has been used for many protection applications, it is included in and covers in the composition that skin uses, on clothes and other type of textile article and among, be included in the transparent plastic container, or the like, be used for resisting the damage and the Degradation of some wavelength light of UV spectrum.Foremost UV light absorber is benzotriazole (can derive from Ciba, trade name is Ting Nafen ), and benzophenone (can derive from Cytec Industries, trade mark is Cyasorb ^TM).These compounds have ultraviolet absorption ability efficiently; But they are very expensive, can prove that they are difficult to be attached in the different destination medias, and they tend to the medium (for example plastics) from some type migration and come out.In addition, there is operational difficulty in these two kinds of well-known UV light absorber, because they make powder usually and use with powder type, and fusing point is lower.Particularly, in plastic medium, the powder type of these compounds can have problems; Operating liquid is much easier, does not need fusing, and more high-level efficiency and mixing fully in whole target plastic are provided.In addition, these previous UV light absorber of using provide the wavelength region of ultraviolet protection narrower ([λ] _MaxWith regard to benzotriazole is about 290 to about 340nm; Be 260 to 300nm with regard to benzophenone), like this, finally left over the latent lesion wavelength region (to about 400nm) of no ultraviolet irradiation protection.For the possible protection that covers this wideer wavelength region is provided; attempt increasing the amount of this ultraviolet radiation absorption immunomodulator compounds; but this is invalid; say nothing of that more substantial UV light absorber like this will increase in the target transparent plastics and other similar application in do not wish painted generation; so that the screening compound of necessary use higher dosage (for example; for instance, bluing agent), so that the antagonism decolorization.Therefore; efficient, liquid UV light absorber need be provided; it presents multifunctionality; this multifunctionality can be attached to or be applied in different and various medium and the matrix, and this UV light absorber can be for providing protection (so that for preventing that possible damage relevant with ultraviolet irradiation and/or degraded from providing best all-round protection) from about 290 to about 400nm UV spectrum wavelength region is whole.

Record and narrate among the European patent abstract 350-0386-A as L ' Oreal SA, compound based on methyne, some malonic ester derivative particularly, in the sunscreen composition of used for cosmetic, it is useful as UV light absorber, usually the cost of its manufacturing is low, and provides ultraviolet protection in the spectrum of the about 360nm of about 280-.Therefore but these compounds are solvable at the organic solvent camber, and when it being imported solids composition for example in the plastics time, it moves easily from this solids composition.Therefore, although may wish very much in plastics, to adopt effective UV light absorber, for example, the malonic ester derivative, but in existing UV light absorber technical field, this was never taught, and was not also clearly proposed, because a kind of so stable and therefore be that there is bigger difficulty in ultra-violet absorption composition efficiently by this raw material production based on methyne.Therefore need to produce cheap UV light absorber, this absorption agent presents requisite in the medium save power (as mentioned above) in the plastics etc. for example, thereby, necessary and protection hope to degrading due to the ultraviolet irradiation is provided.

For the further exploitation that ultraviolet protection carried out of some polymeric media (for example polyester) has comprised compound based on Vanillin and Resorcinol, aspect low separating out from this thermoplastics, this compound will be that effectively this compound must be imported into during the actual polyreaction of matrix thermoplastic polymer itself.For example, the United States Patent (USP) 4617374 of authorizing people such as Pruett has been instructed for the final this UV light absorber of using of polyester.But again, this compound presents the very high consequence of separating out, unless in polymerization procedure they are added with polyester monocase as preparing the polymeric reactant itself.In a such example, these UV light absorber not only are mixed in this thermoplastic medium, and in fact become one in polymkeric substance.Similarly, though these compounds present chromatic effect really when polymerization in target polyesters, unfortunately, the multifunctionality of these compounds is limited to, and only be the opportunity of these compounds of importing during above-mentioned polymerization process because allow effectively.Therefore, still needing provides more polyfunctional UV light absorber for the final application of thermoplasticity, this UV light absorber of importing whenever that makes that the producer can be during the productive target thermoplastic material, thereby this additive does not show so high separating out, and still provides excellent UV absorbing properties to it.

Have now found that,,, particularly relate to above-mentioned hanging down when separating out sexual needs for novel UV absorbers provides may using of greater functionality by on some ultraviolet radiation absorption immunomodulator compounds, adding polyoxyalkylene chain.Therefore, the compound that has been found that this polyoxy alkylene (polyoxyalkylenated) (for example, but do not limit scope of the invention ground, employing is based on the compound of Vanillin and resorcinol group) UV light absorber is provided, these absorption agents are at whole wide bands of a spectrum ([λ] _MaxBe about 280 to about 400nm, more preferably from about 320 arrive about 400nm) last deleterious UV-A of high efficiency filter and UV-B ray.And, have been found that and benzotriazole and/or dihydroxy benaophenonel, or the ultraviolet radiation absorption immunomodulator compounds of other similar type combines the composition of generation thereby prevent a large amount of potential damages of (from about 250 to about 400nm) uviolizing.In addition, this to be combined in required medium camber stable, and therefore provide long-effective protection to the required sample that is stored in the target processing plastics.And, when preparing according to some operation, the most noticeable when being to use some alkoxylating catalyst, the colour of these compounds is very low, described alkoxylating catalyst non-exclusively comprises, the phosphoric acid salt of metal hydroxides and other alkali (both separately and be present in the alkoxylating catalyst based on amine (especially having the acquisition proton affinity)) and rare earth metal, for example United States Patent (USP) 5 of Edwards, those of teaching in 057,627.Thereby these low colour surrogates are effectively to utilize during colourless (limpid and transparent) used to provide the foundation, for example, required transparent plastics, it provides essential effective ultraviolet protection simultaneously.

Though it is verified based on the ultraviolet radiation absorption immunomodulator compounds of methyne (promptly at some, the malonate derivative of L ' Oreal) some effects have been obtained in the field, but also there is not openly or advises using clearly the polyoxyalkylenated derivative of these UV light absorber so far, openly (for example be not used for some medium about them, for instance, plastics), perhaps in (for example skin, textiles) on other surface or the ability in other application (for example printing ink etc.).Particularly, still unexposed relevant low colour, low polyoxy alkylene ultraviolet radiation absorption immunomodulator compounds of separating out (transport property), these compounds provide wavelength between the effective protection of about 320nm to the ultraviolet irradiation between about 400nm.Therefore; in UV light absorber market and the most particularly; there is very large demand at overlay and container (being used for storing and protection food, pill etc.) market; because these types are improved and are combined than inexpensive materials and method, and these materials and method are provided by the polyoxyalkylenated ultraviolet radiation absorption immunomodulator compounds based on methyne of the present invention.

Developed or improved other ultraviolet-absorbing compound and composition of being used for some (thermoplasticity, thermoset etc.) plastic applications, for example deriving from Ciba company is that people know and an as above-mentioned compounds with title Ting Nafen .Though these compounds appear as any liquid of storing in plastics itself and the container with these plastics manufacturings, solid etc. extraordinary ultraviolet protection is provided, unfortunately, this compounds shows defective unfavorable or that have problems.Particularly, use these compounds, the width that obtains protecting in the UV spectrum is generally limited to about 320nm to about 375nm.Therefore, to some plastics packed content, they can not provide enough ultraviolet protections of covers entire ultraviolet line wavelength region usually.And the general normality of the compound of these Ciba is a solid, and therefore or with pressed powder is distributed in the target resin, perhaps must near the branch timing it be dispersed in the liquid so that it proves effective very much by the final user.If the UV light absorber of any this Ciba is actual is liquid, and then they still exist limitation on the wavelength region width of relevant ultraviolet protection.At last, and most important ground, the compound of these Ciba shows higher from target plastic resin, particularly thermoplastics, for example level of separating out in the polyethylene terephthalate and migrate attribute.Therefore, although these compounds effectively protect the ultraviolet ray of some scope, having many defectives, is highly to need and essential to its improvement.Therefore, up to the present, being starved of provides the efficient UV light absorber of eliminating above defective.

Goal of the invention

Therefore, the objective of the invention is, (for example provide novel low colour, low thermoplasticity migration, low separating out) ultraviolet-absorbing compound, these compounds may further be liquid when pure with it, undiluted state when existing under room temperature, and it provides ultraviolet protection on the wide wavelength region up to 390nm at least.Further purpose of the present invention is; a kind of UV light absorber of polymkeric substance is provided, and it can be used for various media, and is used on the different base materials; as ultraviolet filtering compound efficiently, perhaps be used in the suitable composition so that protection is not subjected to ultraviolet potential injury.Further purpose of the present invention is, the UV light absorber based on methyne is provided, and this absorption agent provides bright and transparent plastics.Still a further object of the present invention is, some polyoxyalkylenated UV light absorber based on methyne is provided, and this absorption agent does not require the bluing agent that has significant quantity so that low-yellowing effect (and therefore brighter transparent sharpness is provided) is provided in transparent thermoplastic is used in target plastic or other medium.Remain another object of the present invention, it provides a kind of ultra-violet absorption composition efficiently or goods, said composition or goods contain low colour of the present invention, low thermoplasticity migration ultraviolet absorber compounds, and particularly when when room temperature is undiluted, compound normality wherein is a liquid.In addition; one of purpose of the present invention is; the low-color ultraviolet absorption agent is provided; this absorption agent provides protection to the content of transparent thermoplastic packing; make and be not easy because of degrading in the ultraviolet ray that is exposed to 250 to 400nm wavelength regions (to work as with a kind of test compound; when for example riboflavin is stored in a transparent thermoplastic containers; the ultraviolet irradiation that is exposed to 250-400 when container is in the time of minimum 20 hours, and riboflavin still keeps it to form by 25% the riboflavin that surpasses original vol in its aqueous solution).The manufacture method of this low-color ultraviolet absorbing compounds also is provided in addition.

Detailed Description Of The Invention

Therefore, the present invention comprises a kind of transparent thermoplastic goods, this thermoplastic article contains at least a ultraviolet absorber compounds, this compound arrives in the whole wavelength region of about 400nm about 300, present ultraviolet absorption characteristic, make described goods present maximum 10% ultraviolet ray transmissivity at 390nm wavelength place; And wherein said at least a compound presents a kind of level of separating out (extraction level) from described thermoplastic article, the absorption level tolerance that it shows after exposing 2 hours with the pure extraction solution of heating, maximum 0.1 absorbance units, preferred 0.05, more preferably 0.025, most preferably be low to moderate 0.0, wherein said UV light absorber contains at least a polyoxyalkylene chain, perhaps alternatively, whenever described UV light absorber is imported in the described thermoplastics during described goods manufacturing wherein, perhaps once more alternatively, wherein said at least a UV light absorber in merging to described thermoplastic article before, and pure at it at room temperature, during undiluted state is liquid.And relevant portion of the present invention is as above-mentioned same transparent thermoplastic article, and wherein said thermoplastic article presents maximum 2.5 yellow degree level and at least 90 luminance level simultaneously.In addition, comprise within the scope of the present invention be a kind of liquid ultraviolet radiation absorption immunomodulator compounds, its Gardner (Gardner) color value is 8 at least, wherein said UV light absorber presents a kind of level of separating out from polyethylene terephthalate, with the absorption horizontal survey that the pure extraction solution that heats shows after exposing 2 hours, maximum 0.1 absorbance units, preferred 0.05, more preferably 0.025, and most preferably be low to moderate 0.0.Further being contained among the present invention is a kind of ultraviolet compound, and it meets the structure of formula (I) representative

R wherein ₁, R ₂, R ₃, R ₄And R ₅Identical or different, and be selected from C _1-20Alkyl, halogen, hydroxyl, hydrogen, cyano group, alkylsulfonyl, sulfo group, sulfato, aryl, nitro, carboxyl, C _1-20Alkoxyl group and B-A, wherein R at least ₁, R ₂, R ₃, R ₄And R ₅In one of be B-A, B is selected from N, O, S, SO here ₂, SO ₃, CO ₂, and A is represented by formula (II)

(II) [alkene oxygen base (alkyleneoxy) component] _zR '

Wherein alkene oxygen base component is selected from C _2-20Alkene oxygen base, R ' is selected from hydrogen, C _1-20Alkoxyl group, C _1-20Alkyl and C _1-20Ester; If wherein B is N, then Z is 2, and if B is not N, then Z is 1; X and Y are identical or different, and are selected from hydrogen, cyano group, C (O) OR, C (O) R, C (O) NR " R , C _1-20Alkyl and C _1-20Alkoxyl group, perhaps X and Y be in conjunction with forming a member ring systems, and R, R " and R  such as above to R ₁, R ₂, R ₃, R ₄And R ₅In arbitrary definition of doing; And if wherein X and Y be not in conjunction with forming a member ring systems, at least one is cyano group or hydrogen among then described X and the Y.Therefore another part and parcel of the present invention is the formation method of low-color ultraviolet absorber compounds and this low-color ultraviolet absorbent compound, and wherein said ultraviolet radiation absorption immunomodulator compounds is consistent with the structure of formula (III) representative:

(III)

Wherein A is represented by formula (II)

(II) [alkene oxygen base component] R '

Wherein alkene oxygen base component is selected from from 1 unit at least a C that reaches 100 repeating units _2-20Alkene oxygen base, Racemic glycidol and any mixture thereof, and R ' is selected from hydrogen, C _1-20Alkoxyl group, C _1-20Alkyl and C _1-20Ester; Wherein this method comprises following sequential steps:

A) in the presence of catalyzer, make the reaction of Vanillin and at least a compound, this at least a compound is selected from the group of being made up of at least a compound, and this compound contains at least one group that contains oxyalkylene, and this group is selected from least a C ₂-C ₂₀Alkylene oxide, Racemic glycidol and any mixture thereof; And

B) make the reaction product of step " a " and at least a cyano group alkyl ester (for example, non-exclusively with ethyl cyanacetate) reaction.Volumetric concentration is 5% in being present in methanol solution, and in the 320-400nm wavelength region during maximal ultraviolet line absorption, this new compound should present the Gardner color level of maximum XX, at this moment 390 and 400nm between each wavelength place, have the ultraviolet ray transmissivity of maximum 10% actual measurement.And at room temperature, under its pure and undiluted state, this new compound also can be liquid, and handled easily and importing in the required medium again, for example, non-exclusively, in the thermoplastics.

And, the present invention includes the formation method of low-color ultraviolet absorbent compound, wherein said ultraviolet radiation absorption immunomodulator compounds is consistent with the structure of formula (IV) representative.

Wherein A is represented by formula (II):

(II) [alkene oxygen base component] R '

Wherein alkene oxygen base component is selected from from 1 unit to the C that reaches 100 repeating units _2-20At least a in alkene oxygen base, Racemic glycidol and any mixture thereof, and R ' is selected from hydrogen, C _1-20Alkoxyl group, C _1-20Alkyl and C _1-20Ester: described method comprises following sequential steps:

A) in the presence of catalyzer, make the reaction of Resorcinol and a kind of compound to make the poly-alkoxylation Resorcinol, this compound is selected from the group of being made up of at least a compound, and this compound contains at least one group that contains oxyalkylene, and this group is selected from least a C ₂-C ₂₀Alkylene oxide, Racemic glycidol and any mixture thereof; And

B) reaction product of step " a " and a kind of compound are reacted, thus, described compound is protected this poly-alkoxylation oh group;

C), the product of step " b " is changed into aromatic aldehyde through producing the Vilsmeier complex compound;

D) subsequently, make aldehyde and a kind of compound reaction of taking off acetyl of step " c ", so that make these poly-alkoxylation oh groups go protection; With

E) subsequently, make the reaction product of step " d " and cyano group alkyl ester (for example, non-exclusively, with ethyl cyanacetate) reaction.

As above structure (III) is defined, volumetric concentration is 5% in being present in methanol solution, and in the 320-400nm wavelength region during maximal ultraviolet line absorption, this new compound should present the Gardner color level of maximum XX, at this moment 390 and 400nm between each wavelength place, have the ultraviolet ray transmissivity of maximum 10% actual measurement.And at room temperature, under its pure and undiluted state, this new compound also can be liquid, and handled easily and importing in the required medium again, for example, non-exclusively, in the thermoplastics.

Contain formula (III) and (IV) this compound compositions be also included among the present invention, particularly contain the composition of these compounds and bluing agent, be used for further importing required molten thermoplastic formulation as liquid or as particle.The invention still further relates to, comprise (I), (III) and (IV) these compound compositions method for making of thermoplastic compounds particularly.

Term " thermoplasticity " is attempted to comprise, presents any synthesizing polymeric material that changes to the physical condition of liquid state from solid-state when being exposed to high enough temp.It should be noted that most in the preferred thermoplastic types of material: polyolefine (that is, polypropylene, polyethylene etc.), polyester (being polyethylene terephthalate etc.), polymeric amide (that is, nylon-1,1, nylon-1,2, nylon-6 or nylon-6,6), polystyrene, urethane, polycarbonate, polyvinylhalide (that is, and polyvinyl chloride and poly-difluoroethylene, this only as an example) etc.Preferred thermoplastics is a polyester among the present invention, and polyethylene terephthalate most preferably.

These thermoplastic articles comprise: bottle, storage vessel, sheet material, film, fiber, plate, flexible pipe, pipe, syringe etc.Included during this enumerates should be transparent flaky resin materials such as polyester, polystyrene, and they are present in the window of intensity and resilience function.For example, low-color ultraviolet absorption agent of the present invention can provide or contribute to the ultraviolet protection with the content excellence of target packing articles, perhaps gives the ultraviolet protection of indoor (for example comprise in tame middle, the buildings of the window that includes this additive, in the automobile) personnel's excellence.Basically, the possible purposes of this low colour, low migration UV light absorber has a lot, and can not easily be developed.But other possible end-use should comprise that solvent system, printing-ink, textile treatment are with composition (on surfaces such as textiles, fiber, fabric or inner).

Other type article that relates to as concrete disclosed transparent, UV protective hot thermoplastic plastic among the present invention still non-exclusively comprises film, sheet material, bottle, container, phial etc.Generally with composition injection molded (or other type molding; for example blowing) during; UV light absorber is added in these compositions; method non-exclusively comprises: by stripping liquid being mixed with resin particle and the whole coating particles of fusion; perhaps by master batch fusing step; at this moment resin and absorption agent pre-mixing, and be combined together to form particulate state.These plastics non-exclusively comprise, polyolefine, polyester, polymeric amide, urethane, polycarbonate and other resin of knowing, for example, in people's such as people's such as Baumgartner United States Patent (USP) 4640690 and Kluger United States Patent (USP) 4507407 under term " thermoplastics " those disclosed resin.Usually, these plastics that comprise the ultraviolet radiation absorption agent addition agent technology such as are extruded through the difference of any amount and are formed, for example, and those disclosed technology in aforesaid U.S. Patent.The preferred thermoplastic plastics are polyester, in an infinite embodiment, are polyethylene terephthalates for example.Therefore, " plastic wrapping " comprises the container that is used to store purpose, sheet material etc., and they comprise the plastics of arbitrary combination as mentioned above.

When term " pure, undiluted state " and ultraviolet-absorbing compound together use, represent these compounds itself without any need for additive just at room temperature in liquid state.Therefore, do not need in these UV light absorber, to add solvent, viscosity modifier and other additive to obtain this physical condition that needs.

These polymeric uv-absorbers of the present invention, as above-mentioned, colour very low (for example, in L-a-b chrominance space (L-a-b scale), do not show be higher than 2.5 yellow value degree).Therefore, need not in concrete UV light absorber, to add other tinting material (for instance), additives such as acid scavenger as bluing agent for low colour (the low yellow degree) characteristic that this needs are provided.Any those of ordinary skill of this area should be very clear, low yellow degree level without any need for other additive existence, this benefit is given specific compound uniquely, and does not represent that any composition that comprises these compounds only contains this innovation compound as thermoplastic additive.In fact, other additive, for example aforementioned bluing agent, acid scavenger, static inhibitor, optical brightener etc. also can import required the finished product medium (for instance, as thermoplastics) before, among and/or add to afterwards in these compounds.

Term " solvent system " comprises the formulation of any moisture or organic liquid.The non-limiting example of estimating Aquo System comprises: washings, sanitising agent, fabric softener, marking ink and tinting material and Keratin sulfate dyestuff.The non-limiting example of organic formulation comprises, non-water washings, sanitising agent, fabric softener, marking ink and tinting material, Keratin sulfate dyestuff and washing agent (descalers), tensio-active agent formulation, hydrocarbon compositions etc.The interpolation of UV light absorber of the present invention is by only adding this liquefied compound in the target solvent system and simultaneously and thoroughly mix and finish.

Marking ink comprises the composition as tinting material, it only is contained in the pen once more as an example, and pen non-exclusively comprises: the toning agent of ballpoint pen and fountain pen, dot-matrix printer, standard duplicating machine, ink jet printing device, permanent indicia pen, do-the erasure pen, newsprinting paper, periodical paper (magazine print), laser inkjet etc.The interpolation of UV light absorber of the present invention is only by adding this fluid cpds in the target marking ink formulation and simultaneously and thoroughly mix and finish.

The term textile treatment composition comprises any formulation of two classes that is applied to (and therefore staying at least one interim ultraviolet-absorbing coating etc. at this textile surface) on the textiles.Also belong to this term in the middle of The compounds of this invention being attached to the fiber of textiles, therefore belong to scope of the present invention.Skin-protecting agent and pigmenting of skin formulation comprise any composition that contains this new ultraviolet absorbing compounds basically, and this compound is used to protect skin to avoid solar radiation.

In view of the present state in present technique field, the benefit that aforementioned novel ultraviolet absorber compounds brings is a lot.For example,, be starved of water white thermoplasticity or thermoset articles, so that identification is included in composition and formulation in these goods for conspicuous reason.For aesthetic purposes, these transparent articles should not show any variable color.Adopt the UV light absorber of the standard of using at present, since the natural characteristics of compound self, their general flavescence, and this natural characteristics provides this color so that absorb in ultraviolet ray range.Therefore, as mentioned, need the bluing agent of high level, so that offset this influence and the colourless resin that needs is provided.Even these compounds may show some flavescence, but the variable color that plastics of the present invention (and The compounds of this invention) do not show this degree, and therefore in target thermoplastic, the bluing agent of usage quantity much less, this provides limpid, the colourless resin that need, provides this appropriate transparent article and the required workload of brighter goods thereby provide cost savings and reduced.Because bluing agent not only helps prevent flavescence in the destination media, and it is tarnished, so generally avoid adopting a large amount of this reagent.Therefore, The compounds of this invention is owing to having the feature of low colour simultaneously, so the sharpness of low grayness level is provided.The result is, required transparent plastics presents the luminance level that can not obtain before this, and (as above-mentioned) gives large-scale and effective ultraviolet protection on wide wavelength region simultaneously.In addition, these effective ultraviolet radiation absorption characteristics effect for some content of protection target thermoplastic storage articles is distinguished.As discussed further below, UV light absorber of the present invention presents the highly ultraviolet radiation absorption characteristic of needs on the wavelength region of the about 400nm of about 300-, to such an extent as to, behind the ultraviolet irradiation of wavelength region 300-400nm, at 20 hours high-intensity ultraviolets (for example and for the experiment of listing below all, at at least 8 whole Sylvania  350 invisible light bulbs, model F40/350BL, each 40 watts) behind the irradiation, the aqueous composition of the riboflavin that exists in the described transparent thermoplastic goods only can show maximum 75% degradation rate.

In addition, these The compounds of this invention present the level of extremely low moving out (for example, low separating out) from plastics and other medium.The polyoxyalkylene chain that exists on it provides purposes abundant ultraviolet absorber compounds, it is as a kind of liquid or low viscosity additive, when importing target thermoplastic, present thoroughly and effectively and mix, and molding subsequently also presents the low-down level of therefrom separating out with cooling.No matter in the importing target thermoplastic when of UV light absorber of the present invention in it is produced, these of product are low separates out level and is represented by described The compounds of this invention (and described thermoplastics of the present invention).Therefore, polymerization stage imports (in the patent as people such as Pruett), and imports in injection phase, perhaps even in the initial mix stages of target thermoplastic and its additive imports, all obtain very low separating out, this is the effect that UV light absorber of the present invention produces.Thisly multi-functional allow the user to set up own reaction method, rather than hang down the restriction of separating out ultraviolet radiation absorption immunomodulator compounds (this is people's such as Pruett situation now) and forcing by effective importing according to other qualification.So give the user a kind of like this handiness benefit, import essential effective UV light absorber neatly in any time of thermoplastics production period.Thus, the ongoing any time of this production method imports to these polymer compounds and becomes convenient in the target resin, because most of polymeric uv-absorber compound of the present invention has the characteristic that is in a liquid state.Thus, operation is greatly improved, and is implemented in dispersion more up hill and dale in the required medium.Again, owing to mix more up hill and dale etc., by adopting these The compounds of this invention, the reliability of its performance and low extracted character aspect while or association, simplicity and reliability obtain increasing, so reduced cost.

In addition, the wider protection of standard UV light absorber that provides at industrial circle than at present also is provided a kind of like this height ultraviolet-absorbing compound reliable, that be easy to processing, low colour and low migration (low separating out).Usually, even increase the amount of this compound in destination media (for example, polyester), these standard UV light absorber only height to about 380nm be effective.Even increase the amount of these standard UV light absorber in destination media (for example thermoplastics), then the variable color meeting in the destination media is more remarkable, does not correspondingly obtain bigger wavelength protection scope simultaneously.On the contrary, The compounds of this invention provides high protection to about 400nm.This effect can be easily through selecting certain chemical substance that is prevalent in storing liquid and the solid to show, it very easily is subjected to, and ultraviolet ray is attacked and decomposition.For example, as following detailed demonstration, riboflavin (vitamins B ₂) satisfy this description; With the standard UV light absorber (for example; Ting Nafen  234) compares; in the aqueous solution and be stored in the transparent polyethylene terephthalate container; and be exposed between 320 and 400nm between following 20 hours of ultraviolet light source, Vanillin of the present invention-and Resorcinol-based compound to give the protection of riboflavin obviously higher.This improvement in conjunction with show any of these The compounds of this invention or whole other characteristics, has shown the novelty and the practicality of these compounds, particularly in transparent and possible plastic applications.

Particularly, these ultraviolet-absorbing compounds of the present invention meet following structure (I)

R wherein ₁, R ₂, R ₃, R ₄And R ₅Identical or different, and be selected from C _1-20Alkyl, halogen, hydroxyl, hydrogen, cyano group, alkylsulfonyl, sulfo group, sulfato, aryl, nitro, carboxyl, C _1-20Alkoxyl group and B-A, wherein B is selected from N, O, S, SO ₂, SO ₃, and A is represented by formula (II)

(II) [alkene oxygen base component] _zR '

Wherein alkene oxygen base component is selected from C _2-20Alkene oxygen base, R ' is selected from hydrogen, C _1-20Alkoxyl group, C _1-20Alkyl and C _1-20Ester; If wherein B is N, then Z is 2, and if B is not N, then Z is 1; X and Y are identical or different, and are selected from hydrogen, cyano group, C (O) OR, C (O) R, C _1-20Alkyl and C _1-20Alkoxyl group, and R such as above to R ₁, R ₂, R ₃, R ₄And R ₅In arbitrary definition of doing; R wherein ₁, R ₂, R ₃, R ₄And R ₅In at least one is B-A; And at least one is cyano group or hydrogen among described X and the Y.Preferably, when X was ester group, Y was a cyano group, and B is O, and preferred olefinic constituent is ethylene oxide, propylene oxide or oxybutylene, and most preferably ethylene oxide and propylene oxide (these monomeric 2-100 unit; Preferred 2-50; Most preferably 5-20); And R ' hydrogen preferably.Therefore these compounds must also show aforementioned low colour and low migration (from destination media, for example moving) characteristic from plastics, and exist as liquid under its undiluted state in room temperature.

Preferably, this low-color ultraviolet absorbing compounds meets with following formula (I), (III) and (IV) structure of representative.These compounds so that as above-mentioned the discussion, are provided the low level of separating out from thermoplastics that needs by the polyoxy alkylene.Provide this structure with the following formula (I) and (III) ability of consistent low colour kind, and therefore, through using the alkoxylating catalyst of particular type, non-Resorcinol based compound is obviously controlled, these catalyzer (for example non-exclusively comprise rare-earth salts, lanthanum orthophosphate), particularly metal hydroxides (for example, potassium hydroxide, both Individual existences, and have a compound, this compound has strong avidity to the free protons and/or the proton that can get in himself reaction medium, below be called " proton sponge ") or the like.The phosphoric acid salt of these catalyzer, particularly rare earth obviously disposes according to a kind of like this mode, and the impurity level that promptly is present in the reaction itself is compared the mode that whether sharply reduces with other standard alkoxylating catalyst (for example sodium hydroxide).(please polish according to needs! ).Not to want to be limited to any specific the principles of science, but prerequisite is the potential adverse reaction that aforementioned proton sponge compound stops the electric proton material of strong band, make its attack that is not subjected to end reaction thing and reaction product, and therefore reduced the generation of electrochromic compound in the final product itself.These proton sponge examples for compounds non-exclusively comprise: 1, two (dimethylamino) naphthalenes, 1 of 8-, two (diethylamino)-2 of 8-, 7-dimethoxy-naphthalene, 4, two (the dimethylamino)-fluorenes, 4 of 5-, two (dimethylamino) phenanthrene of 5-, quino-[7,8-is just] quinoline etc., wherein preferred 1, two (dimethylamino) naphthalenes of 8-.Preferably, oxyalkylated compound comprises oxyethane or propylene oxide, and perhaps the two mixture has 2 to about 100 chain length on it; More preferably has about 2 to about 50 chain length; And a kind of chain length of 5 to about 10 most preferably from about, however, still more preferably oxyethane.Therefore, therefore the ultraviolet absorber compounds based on Vanillin of formula (III) structure is the preferred embodiment of formula (I) structure.

The structure consistent with formula (IV) be the embodiment of preferred formula (I) structure also; it is made through Vilsmeier complexing and deacetylated subsequently this compound as the modification formylation of low colour poly-(oxygen alkylene thing (oxyalkylenates)) through above-mentioned hydroxyl protection alkoxylate Resorcinol.In this example, initial alkoxylate can be carried out through catalysis with the alkoxylating catalyst of standard.Again, as above about formula (I) and (III) oxyalkylene of the same type of structure and its chain length equally by preferably as the structure of formula (IV).Therefore the parent material of making in the method for this compound is any compound based on Resorcinol, preferred Resorcinol itself.After alkoxylate, the compound of generation and protectiveness compound react, so that discharge the hydroxyl on it.This protectiveness compound can be ester acid anhydride, preferably C ₁-C ₂₀At least a in the ester acid anhydride, more preferably acetic anhydride.Then; the compound that is protected Vilsmeier complex compound formylation; this complex compound is by for example N; dinethylformamide and phosphoryl chloride form, and can be any such n-compounds, certainly; it non-exclusively comprises ... any other aldehyde-formation group will play a role in the method, so that produced a kind of aromatic aldehyde [for example, Resorcinol (6 moles of ethylene oxide aka EO) diacetic acid esters] based on protecting Resorcinol polyoxy alkylene compound.In order to obtain low colour aldehyde product, under low temperature more (promptly 70 ℃ to 90 ℃), carry out formylation reaction, and the Hypophosporous Acid, 50 existence is arranged.Hypophosporous Acid, 50 is the reductive agent of knowing, and believes that there is the formation that suppresses high painted oxide kind in it.Therefore, it also is very crucial during reaction getting rid of oxygen.After aldehyde forms, make protected hydroxyl go protection by basic hydrolysis.

Contain these compound compositions and be also included among the present invention, particularly those are as liquid or particulate compound and bluing agent.The compound of these broad definition and so more specifically type provide (again with regard to the essential feature of low colour, low migration, liquid state and the clear applications with regard to effectively and completely mixing in the destination media, transparent plastics is as an infinite example).

The appropriate amount height that uses in different compositions and the application depends on each of those independent possibilities.Therefore, for example in the plastics, the add-on of UV light absorber of the present invention is that about 0.001-of plastics composite gross weight is about 1.5%, and preferably about 0.01-is about 1.0%, and 0.05-about 0.5% most preferably from about.These plastics can comprise other standard additive, comprise antioxidant, finings, nucleator, acid scavenger, spices, tinting material (for transparent, only being used for painted), static inhibitor or the like.

Preferred embodiment is described

Preferred innovation UV light absorber, the general method of its manufacturing and use is as follows:

The preparation of compound

Embodiment 1

In autoclave, add 2280 gram Vanillins, 20 gram lanthanum phosphate catalyst.Then, seal this autoclave,, be pressurized to 34.45kPa (5PSIG) nitrogen then with purging with nitrogen gas several (reaching 413.4kPa (60PSIG) pressure).Autoclave being heated to after 121 ℃, in reaction mixture, add oxyethane, be 3960 grams up to add total amount through for some time.In case added whole oxyethane, with amounting to 30 minutes with boiling behind this mixture.Then, mixture is cooled to 93 ℃, and under the pressure condition that reduces, carried out stripping, so that remove unreacted oxyethane with 15 minutes.Product is that light yellow liquid and hydroxyl value are 134.

Will derive from the gram of 938 in above-mentioned reaction 4-polyoxyalkylene-3-methoxyl group-phenyl aldehyde, 30 gram vitamin-Es, 8 gram glycine, 150 gram water and 305 gram ethyl cyanacetates are loaded in 5 liters the three neck round-bottomed flasks.In the presence of nitrogen atmosphere,, and be incubated 3 hours with this mixture heating up to 70 ℃.When cool to room temperature, add 2500ml water and with mixture heating up to 75 ℃.After treating phase-splitting, once more with 2500ml water flushing product layer.Except that anhydrating, obtain 862 gram products, the λ of this product in the methyl alcohol by rotary evaporation (rotovap) _MaxBe 358nm.Its colour is 41abs/g/l in the methyl alcohol, and this value defined is the absorption of every gram sample in the 1000ml methyl alcohol.

Then, UV light absorber 1000 grams and 5 grams are derived from Milliken ﹠amp; The ClearTint  PC Violet 480 (a kind of bluing agent) of Company mixes.Then this UV mixture is used for application test.

Embodiment 2

In 456 gram Vanillins, 1 gram KOH thin slice and 4 gram proton sponges [1, two (dimethylamino) naphthalenes of the 8-] autoclave of packing into.Then, seal this autoclave,, be pressurized to 34.45kPa (5PSIG) nitrogen then with purging with nitrogen gas several (reaching 413.4kPa (60PSIG) pressure).Autoclave being heated to after 121 ℃, in reaction mixture, add oxyethane, be 792 grams up to add total amount through for some time.In case added whole oxyethane, with amounting to 30 minutes with boiling behind this mixture.Then, mixture is cooled to 93 ℃, and under the pressure condition that reduces, carried out stripping, so that remove unreacted oxyethane with 15 minutes.Obtain 1253 gram products (productive rate is 97%), product is that light yellow liquid and hydroxyl value are 142.

Will derive from the gram of 100.4 in above-mentioned reaction 4-polyoxyalkylene-3-methoxyl group-phenyl aldehyde, 0.82 gram vitamin-E, 0.92 gram glycine, 20 gram water and 26.3 gram ethyl cyanacetates are loaded in 250 milliliters the three neck round-bottomed flasks.In the presence of nitrogen atmosphere,, and be incubated 3 hours with this mixture heating up to 70 ℃.When cool to room temperature, add 150ml water and with mixture heating up to 75 ℃.After treating phase-splitting, once more with 150ml water flushing product layer.Remove with rotary evaporation anhydrate after, with the MeOH dilution raffinate of 200ml.Then, filter this mixture, obtain 80 gram weak yellow liquid products, the λ of this product in the methyl alcohol through 5 micron filters _MaxBe 360nm.Its colour is 42abs/g/l in the methyl alcohol, and this value defined is the absorption of every gram sample in the 1000ml methyl alcohol.

Then, this UV light absorber 1000 grams are derived from Milliken ﹠amp with 5 grams; The ClearTint  PC Violet 480 of Company mixes.Then this UV mixture is used for application test.

Embodiment 3

In 1830 gram 4-hydroxy benzaldehydes, 20 gram lanthanum phosphate catalyst (as using among the above embodiment 1) autoclave of packing into.Then, seal this autoclave,, be pressurized to 34.45kPa (5PSIG) nitrogen then with purging with nitrogen gas several (reaching 413.4kPa (60PSIG) pressure).Autoclave being heated to after 121 ℃, in reaction mixture, add oxyethane, be 3960 grams up to add total amount through for some time.In case added whole oxyethane, with amounting to 30 minutes with boiling behind this mixture.Then, mixture is cooled to 93 ℃, and coupling vacuum stripping 15 minutes, so that remove unreacted oxyethane.Product is that light yellow liquid and hydroxyl value are 144.

Will derive from the gram of 860 in above-mentioned reaction 4-polyoxyalkylene-phenyl aldehyde, 30 gram vitamin-Es, 8 gram glycine, 150 gram water and 305 gram ethyl cyanacetates are packed in 5 liters the three neck round-bottomed flasks.In the presence of nitrogen atmosphere,, and be incubated 3 hours with this mixture heating up to 70 ℃.When cool to room temperature, add 2500ml water and with mixture heating up to 75 ℃.After treating phase-splitting, once more with 2500ml water flushing product layer.Remove with rotary evaporation anhydrate after, obtain 862 gram products, its λ in methyl alcohol _MaxBe 338nm.

Embodiment 4

800 gram Resorcinols, 400 gram toluene and 4 gram sodium hydrate particles are packed in the autoclave.Then, seal this autoclave,, be pressurized to 34.45kPa (5PSIG) nitrogen then with purging with nitrogen gas several (reaching 413.4kPa (60PSIG) pressure).Autoclave being heated to after 121 ℃, in reaction mixture, add oxyethane, be 1920 grams up to add total amount through for some time.In case added whole oxyethane, with amounting to 30 minutes with boiling behind this mixture.Then, in 100 ℃ this mixture is carried out stripping, so that remove unreacted oxyethane and toluene (adding water termly) so that help to remove toluene through rotary evaporation.The hydroxyl value of final product is 304.

Will derive from the gram of 266 in above-mentioned reaction polyoxyalkylene Resorcinol, 193 gram diacetyl oxides and 2 gram N-Methylimidazoles are packed in 1 liter the three neck round-bottomed flasks.In the presence of nitrogen atmosphere,, and be incubated 3 hours with this mixture heating up to 130 ℃.When cool to room temperature, mixture is transferred to one 2 be raised in single neck round-bottomed flask, and add 200 gram water.In 100 ℃ this mixture is carried out stripping through rotary evaporation, so that remove the acetic acid by product.After removing acetic acid, stay 310 gram polyoxyalkylene resorcin diacetates.

In 5 liters three-necked flask, pack into 915 the gram N, dinethylformamide.When carrying out purging with nitrogen gas, in these 5 liters of flasks, add the Hypophosporous Acid, 50 of 34 grams 50%.The mixture that obtains is cooled to-5 ℃, at this moment, 664 gram phosphoryl chlorides (phosphorous oxychloride) is slowly added the while storage temperature between-5 and 0 ℃.The Vilsmeier complex compound that obtains added in the mixture (follow purging with nitrogen gas), this mixture is the diacetyl oxides of 1138 gram polyoxyalkylene resorcin diacetates, 28 gram 50% Hypophosporous Acid, 50 and 30 grams.Add during the Vilsmeier complex compound, temperature is no more than 25 ℃.In case finish interpolation, heating this mixture to 70 ℃ under nitrogen atmosphere, and be incubated 2 hours.Subsequently, with this mixture cool to room temperature, and add a kind of solution, this solution contains the sodium hydroxide solution of 2492 gram water and 1566 grams 50%.Under nitrogen atmosphere with this mixture heating up to 75 ℃ and phase-splitting.Product layer is mixed with the sodium hydroxide solution of 876 gram water, 546 grams 50% and 45% potassium hydroxide solution of 92 grams.Under nitrogen atmosphere protection, with this mixture heating up to 70 ℃ and be incubated 3 hours.Behind cool to room temperature, after its pH that neutralizes with 93% sulphuric acid soln is 7,1000 water that restrain are added in this mixture.Under nitrogen atmosphere with gained mixture heating up to 75 ℃ and phase-splitting.This product layer of stripping, and make it pass through a strainer, filter the light yellow liquids of 880 grams.The Gardner color value of 5% methanol solution of this liquid (1953 series) is 6.The infrared spectra of this product demonstrates the peak (the aldehyde carbonyl stretches the peak) of a 1670cm.In methyl alcohol, the λ of this material _MaxBe 273nm, in addition, second peak is at the 312nm place.

In the three neck round-bottomed flasks of 500ml, add 2 of 91 grams derive from above-mentioned reaction, 4-polyoxyalkylene phenyl aldehyde, the glycine of 3 gram vitamin-Es, 0.85 gram, 31 gram ethyl cyanacetates and 20 gram water.In nitrogen atmosphere protection, reaction mixture is heated to 70 ℃ and be incubated 3 hours.After with the mixture cool to room temperature, add 250 gram water, and mixture is heated to 75 ℃ under nitrogen atmosphere.Once more with the product of these phase-splittings of water washing of 250 grams.When separating each phase or stripping, remaining 95 gram products.In methyl alcohol, the λ of this material _MaxBe 367nm.

This UV light absorber 1000 grams are derived from Milliken ﹠amp with 8 grams; The ClearTint  PC Violet 480 of Company mixes.Then this UV mixture is used for application test.

Comparative Examples 1

In autoclave, add 2280 gram Vanillins, 20 gram sodium hydroxide catalysts.Then, seal this autoclave,, be pressurized to 34.45kPa (5PSIG) nitrogen then with purging with nitrogen gas several (reaching 413.4kPa (60PSIG) pressure).Autoclave being heated to after 121 ℃, in reaction mixture, add oxyethane, be 3960 grams up to add total amount through for some time.In case added whole oxyethane, with amounting to 30 minutes with boiling behind this mixture.Then, mixture is cooled to 93 ℃, and coupling vacuum stripping 15 minutes, so that remove unreacted oxyethane.Product is that amber color liquid and hydroxyl value are 134.

Will derive from the gram of 938 in above-mentioned reaction 4-polyoxyalkylene-3-methoxyl group-phenyl aldehyde, 30 gram vitamin-Es, 8 gram glycine, 150 gram water and 305 gram ethyl cyanacetates are loaded in 5 liters the three neck round-bottomed flasks.In the presence of nitrogen atmosphere,, and be incubated 3 hours with this mixture heating up to 70 ℃.When cool to room temperature, add 2500ml water and with mixture heating up to 75 ℃.After treating phase-splitting, once more with 2500ml water flushing product layer.Except that anhydrating, obtain 862 gram products, the λ of this product in the methyl alcohol by rotary evaporation _MaxBe 358nm.Its colour is 25abs/g/l in the methyl alcohol, and this value defined is the absorption of every gram sample in the 1000ml methyl alcohol.

Comparative Examples 2

In the three-necked flask of 500ml, pack into 135 the gram N, dinethylformamide is also used purging with nitrogen gas.In case be cooled to-5 ℃, just the slow adding of 99 gram phosphoryl chlorides (phosphorous oxychloride) maintained the temperature between-5 and 0 ℃ simultaneously.The Vilsmeier complex compound that obtains added in the mixture (cross with purging with nitrogen gas), this mixture is the mixture of 169 gram polyoxyalkylene (6EO) resorcin diacetates and 4.5 gram diacetyl oxides.Add during the Vilsmeier complex compound, temperature is no more than 25 ℃.In case finish interpolation, heating this mixture to 70 ℃ under nitrogen atmosphere, and be incubated 2 hours.Subsequently, with this mixture cool to room temperature, and add a kind of solution, this solution contains the sodium hydroxide solution of 369 gram water and 232 grams 50%.Under nitrogen atmosphere with this mixture heating up to 75 ℃ and phase-splitting.The sodium hydroxide solution of product layer and 153 gram water, 95 grams 50% and the 45% potassium hydroxide solution combination of 16 grams.Under nitrogen atmosphere protection, with this mixture heating up to 70 ℃ and be incubated 3 hours.Behind cool to room temperature, after its pH that neutralizes with 93% sulphuric acid soln is 7,112 water that restrain are added in this mixture.Under nitrogen atmosphere with gained mixture heating up to 75 ℃ and phase-splitting.This product layer of stripping, and make it pass through a strainer, filter the greenish orange look liquid of 110 grams.The Gardner color value of 5% aqueous solution of this liquid (1953 series) is 7.

Comparative Examples 3

In the three-necked flask of 500ml, pack into 135 the gram N, dinethylformamide is also used purging with nitrogen gas.In case be cooled to-5 ℃, just the slow adding of 99 gram phosphoryl chlorides (phosphorous oxychloride) maintained the temperature between-5 and 0 ℃ simultaneously.The Vilsmeier complex compound that obtains added in the mixture (cross with purging with nitrogen gas), this mixture is the mixture of 169 gram polyoxyalkylene (6EO) resorcin diacetates and 4.5 gram diacetyl oxides.Add during the Vilsmeier complex compound, temperature is no more than 25 ℃.In case finish interpolation, heating this mixture to 90 ℃ under nitrogen atmosphere, and be incubated 2 hours.Subsequently, with this mixture cool to room temperature, and add a kind of solution, this solution contains the sodium hydroxide solution of 369 gram water and 232 grams 50%.Under nitrogen atmosphere with this mixture heating up to 75 ℃ and phase-splitting.The sodium hydroxide solution of product layer and 153 gram water, 95 grams 50% and the 45% potassium hydroxide solution combination of 16 grams.Under nitrogen atmosphere protection, with this mixture heating up to 95 ℃ and be incubated 3 hours.Behind cool to room temperature, with 93% sulphuric acid soln this mixture is neutralized after pH is 7, the water of 112 grams are added in this mixture.Under nitrogen atmosphere with gained mixture heating up to 75 ℃ and phase-splitting.This product layer of stripping, and make it pass through a strainer, filter the dark red brown liquids of 110 grams.The Gardner color value of 5% methanol solution of this liquid (1953 series) is 13.

Comparative Examples 4

In the 500ml three-necked flask, add 136 gram N, dinethylformamide.In the nitrogen atmosphere purge, in this 500ml flask, add the Hypophosporous Acid, 50 of 5.2 grams 50%.The mixture of gained is cooled to-5 ℃, at this moment the slow adding of 99 gram phosphoryl chlorides is maintained the temperature between-5 and 0 ℃ simultaneously.The Vilsmeier complex compound that obtains added in the mixture (cross with purging with nitrogen gas), this mixture is the mixture of 170 gram polyoxyalkylene (6EO) resorcin diacetates, 4.2 gram 50% Hypophosporous Acid, 50 and 4.5 gram diacetyl oxides.Add during the Vilsmeier complex compound, temperature is no more than 25 ℃.In case finish interpolation, heating this mixture to 90 ℃ under nitrogen atmosphere, and be incubated 2 hours.Subsequently, with this mixture cool to room temperature, and add a kind of solution, this solution contains the sodium hydroxide solution of 369 gram water and 233 grams 50%.Under nitrogen atmosphere with this mixture heating up to 75 ℃ and phase-splitting.The sodium hydroxide solution of product layer and 153 gram water, 95 grams 50% and the 45% potassium hydroxide solution combination of 16 grams.Under nitrogen atmosphere protection, with this mixture heating up to 95 ℃ and be incubated 3 hours.Behind cool to room temperature, with 93% sulphuric acid soln this mixture is neutralized after pH is 7, the water of 112 grams are added in this mixture.Under nitrogen atmosphere with gained mixture heating up to 75 ℃ and phase-splitting.This product layer of stripping, and make it pass through a strainer, filter the dark red brown liquids of 100 grams.The Gardner color value of 5% methanol solution of this liquid (1953 series) is 11.

Comparative Examples 5

[0067] with the right-formyl-N of 1000 grams, N-polyoxyethylene aniline (7 moles of EO) mixes with 124 parts of diethyl malonates and 30 parts of volatile salts.Then, this mixture of heating continues 10 hours between 70 and 75 ℃.Ultraviolet ray-visible light (UV-Visspectra) with this mixture is monitored this reaction.As indicated (A/gl=20.1) of absorption peak that occurs at the 377nm place, when reaction is finished, follow further this product of stripping under the pressure that reduces, so that obtain the finished product.

Comparative Examples 6

In the three-necked flask of 250ml, add 17 grams 3,4-dimethoxy benzaldehyde, 70ml toluene, 1 gram piperidines and 15 gram ethyl cyanacetates.In the presence of nitrogen atmosphere, with this mixture heating up to 110 ℃ and be incubated 2 hours.Form precipitation during cooling.Toluene by 1: 1: acetone soln is collected and this throw out of recrystallization.In being set at 70 ℃ baking oven after the drying, the solid of residue pistac, its λ in methyl alcohol _MaxBe 357nm.

Comparative Examples 7

In the three-necked flask of 250ml, add 17 grams 2,4-dimethoxy benzaldehyde, 70ml toluene, 1 gram piperidines and 15 gram ethyl cyanacetates.In the presence of nitrogen atmosphere, with this mixture heating up to 110 ℃ and be incubated 2 hours.Form precipitation during cooling.Toluene by 1: 1: acetone is collected and this throw out of recrystallization.In being set at 70 ℃ baking oven, after the drying, remain yellow spicule.The λ that contains the methanol solution of this material _MaxBe 368nm.

Comparative Examples 8 and 9

Synthesizing of Vanillin UVA typical compound-ethyl 2-cyano group-3 (4-hydroxyl-3-methoxyphenyl) acrylate (propenoate)

Method A

In the 250ml three neck round-bottomed flasks that have been equipped with reflux exchanger, mix Vanillin (15.2 gram, 0.1 mole), ethyl cyanacetate (12.5 grams, 1.1eq) and ethanol (100ml).When stirring, add piperidines (1.5 gram) and all mixtures and refluxed 2 hours.Behind cool to room temperature, the HCl with 10% is acidified to pH 5-6 with mixture.Collect formed throw out by filtering, for several times with methanol wash.And at air drying producing glassy yellow crystallized product (9 gram), this product is absorbed as 360nm in the acetone.

Method B

In the 250ml three neck round-bottomed flasks that have been equipped with reflux exchanger, mix Vanillin (15.2g, 0.1 mole), ethyl cyanacetate (12.5 grams, 1.1eq) and toluene (100 milliliters).When stirring, add piperidines (1.5 gram) and all mixtures and refluxed 2 hours.Behind cool to room temperature, with several 10% HCl with the mixture acidifying.Collect formed throw out by filtering, for several times with methanol wash.And at air drying producing yellow crystalline product (19.2 gram), this product is absorbed as 360nm in the acetone.

The commercial sample of Ting Nafen  234 derives from Ciba.Equally, obtain and test the Eastman Heatwave  ultraviolet ray enriched material sample that is used for the comparison purpose.Then, these commercial sample are imported in some thermoplasticity finished product, as other Comparative Examples in the above-mentioned Comparative Examples.In fact the Eastman UV light absorber is carried out polymerization by this UV light absorber and thermoplast itself and is imported.The UV light absorber of this Ciba adds in the fused thermoplasticity formulation with powder, thoroughly is blended in wherein then.

The preparation of thermoplastic compounds

For example import this UV light absorber in the injection molding method operation of polyethylene terephthalate at the polyester thermoplastics.In a chamber through stir stripping liquid is blended into heat, on exsiccant (particulate state) polyethylene terephthalate resin, resin is to the absorption minimum of moisture.Absorption agent and particulate blend are fed the feed throat of machine in the mode of gravity charging.At this feed zone, finish fusion (conducting heat) from the sleeve pipe of machine by the screw extrusion press that adopts the rotation of heating.The rotation of screw rod thoroughly mixes absorption agent and molten resin, produces uniform plastic melt, this melt is expelled in the mold, so that form intermediary thermoplastic article, for example parison.

Carrying out further first being processed, making intermediate (for example parison) balance under normal room temperature and humidity.Goods are placed on Infrared heaters working face the place ahead, and this makes the temperature of parison be increased to its softening temperature.Then, warmed-up parison is transferred in the mold, at this rod is inserted in this parison, an end of this parison that stretches arrives the bottom of this mold.Subsequently, pressurized air is blown in the tensile parison, each wall of parison is pushed against in the mold, to form required thermoplastic article, for example, the bottle of the about 15-20 mil of mean thickness.

The transmitance data of vibrin

On the Perkin-Elmer Lambda 35 UV-Vis spectrometers that adopt the 50mm integrating sphere, measure 5 different PET bottle wall parts by the ultraviolet percentage that sees through.The wall thickness of all samples is about 0.43mm (17 mil).The data of ultraviolet ray transmissivity are summarised in the table 2.

Table 1

Be used for the PET bottle that ultraviolet ray sees through test

The bottle sign	The UV light absorber and the composition that add
		A (blank test)	Do not have
B (simultaneous test)	1000ppm receives in the court of a feudal ruler fragrant  234
		C (simultaneous test)	Eastman Heatwave  UV light absorber (from Comparative Examples 8)
D	1000ppm embodiment's 3
		E	1000ppm embodiment's 1
F	Ting Nafen  234 1000ppm embodiment 2 and 1000ppm
		G	1000ppm embodiment 2 with 500ppm embodiment's 1
H	1000ppm Comparative Examples 1
		I	1000ppm Comparative Examples 2

Measuring the transmitted spectrum of PET bottle wall part, from 250nm to 450nm, is increment with 5nm.The result is as follows:

Table 2

Ultraviolet is by being tried the transmitance % of PET resin bottle
						Wavelength (nm)	A	B	C	D	E
250	0.679	0.216	0.204	0.051	0.139
						255	0.71	0.166	0.142	0.013	0.128
260	0.721	0.136	0.078	-0.025	0.078
						265	0.734	0.136	0.174	-0.017	0.050
270	0.816	0.132	0.162	-0.133	0.058
						275	0.835	0.122	-0.002	-0.116	-0.077
280	0.843	-0.045	-0.155	-0.035	0.028
						285	0.734	0.122	-0.123	-0.104	-0.074
290	0.702	0.089	0.053	-0.092	-0.080
						295	0.555	0.039	0.011	-0.175	-0.054
300	0.549	-0.017	0.006	-0.122	-0.089
						305	0.446	-0.004	-0.025	-0.070	-0.119
310	0.656	0.068	-0.079	-0.150	-0.114
						315	0.851	0.013	0.050	-0.058	0.026
320	6.071	0.436	0.206	0.718	0.780
						325	37.58	2.617	0.220	5.514	3.692
330	57.683	3.501	-0.330	7.907	4.931
						335	64.309	3.159	-0.070	7.553	4.983
340	67.429	2.602	-0.069	5.948	4.161
						345	70.121	2.265	0.074	4.180	3.130
350	72.762	2.236	0.070	2.785	2.300
						355	74.583	2.500	0.041	1.868	1.728
360	76.104	3.261	0.095	1.328	1.368
						365	78.368	4.853	0.093	1.040	1.267
370	80.465	7.642	0.426	0.930	1.207
						375	81.829	12.652	2.074	0.916	1.317
380	82.801	21.659	8.993	1.215	1.659
						385	83.594	35.960	26.268	1.902	2.530
390	83.953	53.233	48.346	3.286	4.718
						395	84.433	67.935	64.050	6.169	9.771
400	84.896	77.356	72.800	12.863	20.208
						405	85.308	82.362	77.255	25.844	36.351
410	85.654	84.707	79.610	43.944	53.844
						415	85.932	85.863	81.020	61.386	67.699
420	86.149	86.466	82.089	73.656	76.392
						425	86.501	86.954	82.985	80.690	81.153
430	86.664	87.217	83.691	84.044	83.497
						435	86.892	87.409	84.207	85.562	84.681
440	87.016	87.570	84.756	86.323	85.345
						445	87.196	87.768	85.045	86.683	85.748
450	87.310	87.868	85.351	86.891	85.931

Because the low more expression performance of transmissivity % is good more, so clearly, on bigger wavelength region, UV light absorber of the present invention provides all-round protection more to target P ET resin.UV light absorber of the present invention on longer wavelength region (370-390nm) provide greatly improved ultraviolet protection.In addition, the PET bottle that only has a UV light absorber of the present invention can be lower than 10% transmissivity standard being lower than on the wavelength of 390nm to satisfy.

The protection content avoids ultraviolet ray to be destroyed

The main purpose that UV light absorber is merged in the PET wrapping material is that the protection content is not subjected to ultraviolet destruction.This demand is more urgent in the food product pack field.Usually known, ultraviolet ray can cause the degraded that various battalion divide, for example various VITAMIN.Have now found that UV light absorber of the present invention is providing bigger improvement with respect to commercial UV light absorber aspect the protectiving ultraviolet infringement.

In human body, vitamin B group has wide and different envelop of function.In the process that blood sugar is converted to energy, can relate to most of vitamin B group.For gestation and the women of lactation and for other people who requires multipotency more for example sportsmen and heavy worker, the meals that are rich in vitamin B group are even more important.Aspect generate energy, Wei ShengsuB2, riboflavin is very important.In milk, in the exsiccant fortifying cereals food and the low fatty acid Ruzhong can find riboflavin.Lack this biostearin and can influence skin and mucous membrane.Though riboflavin is very stable to heat, it is very responsive to light.It is especially to ultraviolet-sensitive.

Carried out a research, so that determine the effectiveness that the PET packing stops Wei ShengsuB2 to be degraded owing to irradiation.By being dissolved into the deionized water of 50mg/L, the stock solution of preparation riboflavin.This stock solution is protected and loses light.Use the PET bottle in (listing in table 1) previous experiment.These PET are bottled to have expired this stock solution.This bottle put into the Q ultraviolet ray of Q plate and quickened climatic test instrument (QUV Acelerated Weathering Tester), and it installs the UVA-351 bulb.Ultraviolet is quickened the selection of light (UVA light) bulb will simulate warehouse, supermarket or other the indoor storage period irradiation to fluorescence.Follow the tracks of the degraded of riboflavin with the absorption monitoring at visible absorption peak, 444nm place.Cover check sample with aluminium foil, accept identical processing then.Testing data is summarised in the table 3.

Table 3

The residual rate % of riboflavin after the illumination

The irradiation time length (hour)
							The bottle sign	0	1	3	5	7	9
A (foliation blank)	100％	100％	100％	100％	100％	100％
							A (irradiation)	100％	73％	25％	6％	3％	＜1％
B	100％	92％	77％	59％	44％	31％
							D	100％	95％	86％	72％	62％	50％
E	100％	96％	85％	70％	60％	48％
							F	100％	100％	89％	81％	73％	62％

Data presentation, the blank sample that aluminium foil covers keeps identical riboflavin concentration.Therefore, degraded causes owing to irradiation fully.All contain UV light absorber PET bottle and show the riboflavin maintenance level more much higher than blank sample.The bottle of these bands UV light absorber of the present invention shows that than the bottle that uses best commercially produced product obviously higher riboflavin keeps level.In all bottles, bottle F shows best content radiation protection.

The colourmetric data of vibrin

Absorb more other UV light absorber of long wavelength though disclose, they make polyester article painted usually.Concerning many packaging application, colourless and transparent container is basic.UV light absorber of the present invention is being given superior ultraviolet screener ability and polyester article is not being obtained exquisite balance aspect painted.

On Gretag-Macbeth ColorEye 7000A type spectrophotometer, measure the colourmetric data of different polyester bottles wall parts.These colourmetric data, particularly, L ^*, the brightness/darkness of expression PET bottle wall part, and b ^*, represent its yellow degree/blue degree, these data are as follows:

Table 4

The colourmetric data of each PET resin

UV light absorber (from above table 1, consumption ppm)	L *	b *
			Embodiment 4 (1000ppm)	93.89	2.10
Embodiment 1 (1000ppm)	93.79	2.22
			Comparative Examples 1 (1258ppm)	95.51	6.25
Comparative Examples 3 (873ppm)	95.33	5.61

Therefore, comparative example table reveals similar L ^*Value (brightness), but yellow Du Genggao (b of while ^*Value).The measurement of these values preferably, L ^*Be at least 90 and b ^*Mostly be most about 2.5, in order to indicating the low-yellowing resin of the very a small amount of grey bluing agent of a kind of band, and therefore obtain very bright outward appearance.

The colourmetric data of liquid UV light absorber

As previously mentioned, colourless extremely important concerning this uses.The inventive method can reduce painted level in UV light absorber of the present invention.In this experiment, UV light absorber is dissolved in the methyl alcohol, make 5% solution.Measure Gardner color.Data are listed in table 5.The Gardner color value is high more, represents that this UV light absorber is possible more painted to it in final PET goods.

Table 5

The Gardner color of uv-absorbing agent sample

Sample (deriving from above example)	The Gardner color value
		1	10
4	11
		Comparative Examples 1	11
Comparative Examples 3	18

Like this, data presentation, the inventive method significantly reduce the color level in the liquid UV light absorber of the present invention

Extraction

Food product pack is to require one of maximum application of ultraviolet protection in the wrapping material.Therefore, showing nonmigratory characteristic under the regular service condition is an important requirement for the colourless UV light absorber of the present invention.Their migration performance is studied with following extraction test.

The preparation of employing standard chemical combination method contains the polyester sheet of ultraviolet radiation absorption additive.The surface-area of each plate is 12.5 in2s.Use ClearTuf  8006 PET (M﹠amp; G Polymers produces) this polyester sheet of resin manufacture, use PEN Hypertuf  (M﹠amp simultaneously; G Polymers produces) preparation PEN plate.

For every kind of additive, carry out according to following extraction process:

With the mimic solvent of 95% ethanolic soln as food.With deionized water dilution USP 200 standard number of degrees straight alcohols, preparation extraction solvent.The stainless steel pressure container of band Teflon  lining top cover (tops) is as the extraction container of this research.In these researchs, adopt 125 gram extraction solvent and 6 plate/containers.Arrange these plates, so that these plates are submerged and all sides are exposed to described extraction solvent.

6 blocks of plates are cut in half, and be placed in the stainless steel extraction container, add the ethanol (being preheating to 70 ℃) of 125 grams 95%.With container sealing and be placed in 70 ℃ the baking oven 2 hours, then, they are taken out then.Subsequently, then these plates are shifted out from extraction container, and make solvent be cooled to envrionment temperature.Then extraction solution is carried out spectrophotometric analysis, so that determine whether from the target resin, to extract any UV light absorber.

The spectrophotometric analysis extract is so that determine to exist or do not exist the tinting material of extraction.Use Beckman  DU 650 spectrophotometers of the cell of band 10.00cm path length.At first use the extract that obtains on the pigmented polyester plate never that instrument is returned to zero.Then, contain the extract that the plate extraction of various additives obtains, determine λ at additive with the photoscanning of ultraviolet ray/visible-range _MaxThe place exists or does not exist detectable peak and corresponding specific absorption.The λ of additive _MaxAbsorption level in place's is high more, and the level of expression extraction is high more.Term " the pure extraction test of heating " is subordinated to when of the present invention, comprises this routine analyzer that interrelates with the present invention.

Gather these and the results are shown in following table 6 and 7.

Table 6

Separate out the result among the PET

Sample UV light absorber (from above example)	Content	Separate out result ([λ] maxThe absorption at place)
			Comparative Examples 6	284ppm	0.62
Comparative Examples 7	272ppm	0.60
			Ting Nafen  234	600ppm	0.20
Comparative Examples 8	200ppm	0.172
			Comparative Examples 9	200ppm	0.179
Embodiment 1	600ppm	0.02
			Embodiment 2	600ppm	Do not measure

Separate out the result among table 7 PEN

The sample sign	Content (Loading)	Separate out result ([λ] maxThe absorption at place)
			Comparative Examples 6	284ppm	0.016
Comparative Examples 7	272ppm	0.030
			Ting Nafen  234	600ppm	0.003
Embodiment 1	600ppm	Non-detectable
			Embodiment 2	600ppm	Non-detectable

Thereby these data presentation go out, and UV light absorber of the present invention shows the level of separating out that significantly reduces than Comparative Examples and commodity UV light absorber.UV light absorber of the present invention is more suitable for the contact of food and uses.In Comparative Examples 8 and 9, as those results that show in the above table 6, it shows, import those absorption agents such as (derive from Pruett people's patent) in the injection moulding stage of target thermoplastic rather than in its actual polymerisation stage, can cause particularly comparing with polymerizability UV light absorber of the present invention well beyond the amount of expecting of separating out.

Although described special characteristic of the present invention, but, people can understand certainly, the invention is not restricted to any concrete structural form or embodiment, because for the technician of the technical field of the invention, can make amendment effectively and can produce other embodiment without doubt based on main points of the present invention.Therefore, appended claims is intended to cover the modification that any combination is in the central feature of the present invention of these claim true intentions, design and scope.

Claims (16)

1. transparent thermoplastic goods, it comprises at least a ultraviolet radiation absorption immunomodulator compounds, this compound presents the ultraviolet radiation absorption characteristic on whole 300 to 400nm wavelength region, so that described goods present maximum 10% ultraviolet ray transmissivity at wavelength 390nm place, and this ultraviolet radiation absorption immunomodulator compounds has the structure shown in the following formula I:

R wherein ₁, R ₂, R ₃, R ₄And R ₅Identical or different, and be selected from C _1-20Alkyl, halogen, hydroxyl, hydrogen, cyano group, alkylsulfonyl, sulfo group, sulfato, aryl, nitro, carboxyl, C _1-20Alkoxyl group and B-A, wherein R at least ₁, R ₂, R ₃, R ₄And R ₅In one of be B-A, B is selected from N, O, S, SO here ₂, SO ₃, CO ₂, and A is represented by formula (II)

(II) [alkene oxygen base component] _zR '

Wherein alkene oxygen base component is selected from C _2-20Alkene oxygen base, R ' is selected from hydrogen, C _1-20Alkoxyl group, C _1-20Alkyl and C _1-20Ester; If wherein B is N, then Z is 2, and if B is not N, then Z is 1; X and Y are identical or different, and are selected from hydrogen, cyano group, C (O) OR, C (O) R, C (O) NR " R , C _1-20Alkyl and C _1-20Alkoxyl group, perhaps X and Y be in conjunction with forming a member ring systems, and R, R " and R  such as above to R ₁, R ₂, R ₃, R ₄And R ₅In arbitrary definition of doing; And if wherein X and Y be not in conjunction with forming a member ring systems, at least one is cyano group or hydrogen among then described X and the Y,

Wherein said at least a compound presents the level of separating out from described thermoplastic article, and the absorption horizontal survey so that the pure extraction solution that heats shows after exposing 2 hours mostly is 0.1 absorbance units most; And wherein said UV light absorber contains at least one polyoxyalkylene chain.

2. the transparent thermoplastic goods of claim 1, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds is presented to the level of separating out of many 0.05 absorbance unitses.

3. the transparent thermoplastic goods of claim 2, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds is presented to the level of separating out of many 0.025 absorbance unitses.

4. the transparent thermoplastic goods of claim 3, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds is presented to the level of separating out of many 0.0 absorbance unitses.

5. in the transparent thermoplastic goods of claim 3, the wherein said UV light absorber described thermoplastics of importing whenever during described production of articles.

6. the transparent thermoplastic goods of claim 5, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds presents the level of separating out of maximum 0.05 absorbance unitses.

7. the transparent thermoplastic goods of claim 6, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds presents the level of separating out of maximum 0.025 absorbance unitses.

8. the transparent thermoplastic goods of claim 7, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds shows the level of separating out of 0.0 absorbance units.

9. the transparent thermoplastic goods of claim 5 wherein during the injection forming step of producing described goods, import to described at least a UV light absorber in the described thermoplastic article.

10. the transparent thermoplastic goods of claim 9, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds presents the level of separating out of maximum 0.05 absorbance unitses.

11. the transparent thermoplastic goods of claim 10, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds presents the level of separating out of maximum 0.025 absorbance unitses.

12. the transparent thermoplastic goods of claim 11, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds shows the level of separating out of 0.0 absorbance units.

13. the transparent thermoplastic goods of claim 1, wherein said at least a UV light absorber in being incorporated into described thermoplastic article before, and be liquid during pure at it at room temperature, undiluted state.

14. the transparent thermoplastic goods of claim 13, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds presents the level of separating out of maximum 0.05 absorbance unitses.

15. the transparent thermoplastic goods of claim 14, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds presents the level of separating out of maximum 0.025 absorbance unitses.

16. the transparent thermoplastic goods of claim 15, wherein when the extraction test that stands to heat in the time of 2 hours, described ultraviolet radiation absorption immunomodulator compounds shows the level of separating out of 0.0 absorbance units.